Superexchange Interaction Research Articles

Built-in electric field-enhanced electron super-exchange interactions for non-radical activation in ultra-thin FeOCl/g-C3N4 nanosheets

Built-in electric field-enhanced electron super-exchange interactions for non-radical activation in ultra-thin FeOCl/g-C3N4 nanosheets

The influence of pre-sintering temperature on the structural, magnetic, and dielectric properties of Sr0.67La0.33Fe11.7Zn0.1Co0.2O19 ferrite

The present study explores the impact of varying heat treatment temperatures on the magnetic properties, structural configuration and dielectric characteristics of Sr0.67La0.33Fe11.7Zn0.1Co0.2O19 ferrite. M-type ferrite was synthesized using the traditional solid-state method, with thermal treatment temperatures incrementally increasing from 1230 °C to 1310 °C. Pure M-phase strontium ferrite was achieved at temperatures above 1250 °C. The ideal pre-sintering temperature was identified as 1270 °C, where several factors coalesced to enhance the magnetic properties, including the completion of the solid-state reaction and the diminution of the easily magnetized c-axis, which together fostered the intensification of the superexchange interaction. At this temperature, the magnetic properties reached their zenith, with a saturation magnetization (Ms) of 84.81 emu/g, a remanence (Br) of 419 mT, and a coercivity (Hcj) of 3301 Oe. Additionally, the dielectric constant was significantly high at low frequencies but rapidly declined with increasing frequency, achieving its optimal performance at 1270 °C.

Enhanced spintronic and electronic properties in MTe2-GdCl2 (M=Mo, W) heterojunctions

Two-dimensional ferromagnetic heterojunctions with direct bandgaps and high Curie temperatures (TC) are promising candidates for applications in nanoelectronics and spintronics. Here, we design a Mo(W)Te₂-GdCl₂ heterojunction by integrating experimentally synthesized monolayer Mo(W)Te₂ with recently predicted ferromagnetic monolayer GdCl2. Our first-principles calculations reveal that these heterojunctions display a type-II (staggered) band alignment with a narrow direct bandgap ranging from 1.10 to 1.23 eV, using the HSE06 method. We have incorporated spin-orbit coupling and conducted Monte Carlo simulations to precisely estimate the magnetic ground states of these systems. We find that spin-orbit coupling plays a crucial role in the valence band splitting at the K-point in both heterojunctions. The magnetic anisotropy, TC, and optical performance of individual monolayers are enhanced within these heterojunctions. Under compressive strain, the TC of the heterojunctions increases significantly, reaching about 278 K at -7 % strain, due to strengthened super-exchange interactions between Gd-d and Cl-p orbitals and enhanced interlayer charge transfer. In addition, the band alignment shifts from type-II to type-I under -3 % compressive strain, while tensile strain maintains the type-II band alignment. Our findings offer a viable pathway for developing ferromagnetic semiconducting heterojunctions suitable for nanoelectronic and spintronic applications.

Imprinted atomic displacements drive spin–orbital order in a vanadate perovskite

AbstractPerovskites with the generic composition ABO3 exhibit an enormous variety of quantum states, such as orbital order, magnetism and superconductivity. Their flexible and comparatively simple structure allows for straightforward chemical substitution and cube-on-cube combination of different compounds in atomically sharp epitaxial heterostructures. Many of the diverse physical properties of perovskites are determined by small deviations from the ideal cubic perovskite structure, which are challenging to control. Here we show that directional imprinting of atomic displacements in the antiferromagnetic Mott insulator YVO3 can be achieved by depositing epitaxial films on different facets of the same isostructural substrate. These facets were chosen such that other well-known control parameters, including lattice and polarity mismatch with the overlayer, remain nearly unchanged. We observe signatures of staggered orbital and magnetic order and demonstrate distinct spin–orbital ordering patterns on different facets. We attribute these results to the influence of specific octahedral rotation and cation displacement patterns, which are imprinted by the substrate facet, on the covalency of the bonds and the superexchange interactions in YVO3. Our results show that substrate-induced templating of lattice distortion patterns constitutes a pathway for materials design beyond established strain-engineering strategies.

Crystal structure, Chemical Bonding, and Magnetism of α-Fe6Ga5: How Local Interactions Shape the Structure and Properties of Intermetallic Compounds.

α-Fe6Ga5 was synthesized from the elements as a polycrystalline powder. Its crystal structure was redetermined by high-resolution powder X-ray diffraction, which showed a complex monoclinic structure of the Fe6Ge5 type. The determined lattice parameters (a = 10.08380(6) Å, b = 7.97071(5) Å, c = 7.70489(5) Å, and β = 108.3062(2)°) differ notably from the previous reports. Despite possessing the same structure type as Fe6Ge5, α-Fe6Ga5 displays several distinctive features, such as short Ga-Ga bonds and distorted Fe layers. According to magnetization measurements, α-Fe6Ga5 is a soft ferromagnet with a high Curie temperature of 760 K, which is in stark contrast to the antiferromagnetic behavior of Fe6Ge5 reported in the literature. The electronic structure of α-Fe6Ga5 was studied theoretically using density functional theory-calculations, which showed the pronouncedly covalent character of the short Fe-Ga and Ga-Ga bonds. Similar calculations were performed for Fe6Ge5, which revealed stronger Fe-Ge interactions, which preclude the formation of short Ge-Ge bonds. In both cases, the theoretical calculations showed ferromagnetic instability, which leads to ferromagnetic ordering only in the case of α-Fe6Ga5, likely due to the different nature of Fe-Ga-Fe and Fe-Ge-Fe superexchange interactions.

Observation of Enhanced Long-Range Ferromagnetic Order in B-Site Ordered Double Perovskite Oxide Cd2CrSbO6.

A B-site ordered double perovskite oxide Cd2CrSbO6 was synthesized under high-pressure and high-temperature conditions. The compound crystallizes to a monoclinic structure with a space group of P21/n. The charge configuration is confirmed to be that of Cd2+/Cr3+/Sb5+. The magnetic Cr3+ ions form a tetrahedral structural frustrated lattice, while a long-range ferromagnetic phase transition is found to occur at TC = 16.5 K arising from the superexchange interaction via the Cr-O-Cd-O-Cr pathway. Electrical transport measurements indicate that Cd2CrSbO6 is an insulator that can be described by the Mott 3D variable range hopping mechanism. First-principles calculations reproduce well the ferromagnetic and insulating ground state of Cd2CrSbO6 with an energy band gap of 1.55 eV. The intrinsic ferromagnetic insulating nature qualifies Cd2CrSbO6 as a promising candidate for possible spintronics applications.

Synthesis and Local Characterization of CoO Nanoparticles in Distinct Phases: Unveiling Polymorphic Structures.

The advancement of functional nanomaterials has become a major focus of recent research, driven by the exceptional properties these materials display compared to their macroscopic (bulk) counterparts. Cobalt oxide nanoparticles (CoO-NPs) stand out primarily for their catalytic and magnetic properties, which can enable a range of technological applications, such as advanced catalysts, drug delivery systems, implants, prosthetics, sensors. However, in addition to the dependence on factors such as size, morphology, and functionalization, the properties of CoO-NPs are significantly influenced by the crystal structure. Therefore, local investigation into the polymorphic structures of CoO at the nanometric scale may provide new insights into the local structural and magnetic characteristics of these systems. In this report, we address the synthesis and local characterization of cobalt oxide (CoO) nanoparticles in the rock-salt cubic fcc-CoO and Wurtzite hpc-CoO phases, obtained through thermal decomposition. We analyze the influence of oleylamine and oleic acid ligands on the structural and morphological control of these systems. The obtained nanoparticles were characterized using conventional techniques such as X-ray diffraction (XRD), transmission electron microscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. Local characterization was carried out by the perturbed angular correlation (PAC) nuclear technique using the radioactive tracer 111In(111Cd). Measurements were conducted at 295 and 10 K to investigate possible magnetic phase transitions in these systems. XRD results confirmed the formation of fcc-CoO and hcp-CoO phases. The phase fcc was obtained with the pair of oleylamine and oleic acid ligands, while the phase hcp phase was synthesized using only oleylamine. Additionally, nanoparticles synthesized with oleylamine and oleic acid exhibited better morphological control compared to those produced with only oleylamine. Raman spectroscopy analyses suggest a phase transformation process resulting in Co3O4. PAC results for hyperfine interactions at the 111In(111Cd) probe nucleus, indicate that the hcp-CoO phase shows smaller hyperfine magnetic interactions (B hf = 1 T) compared to the fcc-CoO phase (B hf = 17 T). This suggests the mechanism of superexchange interactions, which are strongly influenced by the Co-O-Co bond angle, which is 110° for the hpc-CoO phase and 180° for the fcc-CoO phase due to the geometries of the systems.

Refrigeration capacity modeling of europium titanate based magnetocaloric compounds using computational single hidden layer intelligent and random forest regression methods

Europium titanate (EuTiO3) is a quantum para-electric magnetocaloric compound with potential application in green magnetic cooling technology. Super-exchange and indirect interactions existing between the magnetic moments of this compound are responsible for the observed magnetic properties such as the refrigeration capacity which falls among the key factors that characterize the usefulness of magnetic system of cooling in addressing energy crisis. Crystallographic substitutions and ionic replacement potentially shift magnetic ordering between anti-ferromagnetism to ferromagnetism and ultimately alters the refrigeration (magnetic) capacity of EuTiO3 compound. This work proposes extreme learning machine (ELM) and random forest regression (RFR) computational approaches to model refrigeration capacity of europium titanate magnetic refrigerant with the aid of applied magnetic field, ionic concentrations and ionic radii predictors. Sigmoid activation based extreme learning machine algorithm(SGA-ELM) demonstrates superior performance over sine function activation based extreme learning machine algorithm(SIA-ELM) with improvement of 0.03 %, 16.04 % and 35.03 % on the basis of Pearson correlation coefficient (CC), root mean square error (RMSE) and mean absolute error (MAE) performance yardsticks, respectively on testing set of EuTiO3 based magnetocaloric compounds. SGA-ELM performs better than SIA-ELM and RFR model with improvement of 35.03 % and 66.84 %, respectively while SIA-ELM model performs better than RFR model with improvement of 59.97 %. SGA-ELM model developed in this work outperforms the existing swarm based support vector regression (SW-SVR) models with performance improvement of 15.38 % (for SW-SVR-Gas with Gaussian function) and 42. 71 % % (for SW-SVR-Pol with polynomial function) using mean absolute deviation (MAD) performance yardstick. Significance of magnetic field and dopants concentrations on refrigeration capacity of different EuTiO3 perovskite was investigated with SGA-ELM model. The accuracy of developed models in determining refrigeration capacity of EuTiO3 compounds would ultimately circumvents experimental challenges and explores future potentials of these classes of compound for addressing present and future energy crisis in cooling industries.

Signatures of the attractive interaction in spin spectra of one-dimensional cuprate chains

Identifying the minimal model for cuprates is crucial for explaining the high-Tc pairing mechanism. Recent photoemission experiments have suggested a significant near-neighbor attractive interaction V in cuprate chains, favoring pairing instability. To determine its strength, we systematically investigate the dynamical spin structure factors S(q,ω) using the density matrix renormalization group. Our analysis quantitatively reveals a notable softening in the two-spinon continuum, particularly evident in the intense spectrum at large momentum. This softening is primarily driven by the renormalization of the superexchange interaction, as determined by a comparison with the slave-boson theory. We also demonstrate the feasibility of detecting this spectral shift in thin-film samples using resonant inelastic x-ray scattering. Therefore, this provides a distinctive fingerprint for the attractive interaction, motivating future experiments to unveil essential ingredients in cuprates. Published by the American Physical Society 2024

Alkali Metals Activated High Entropy Double Perovskites for Boosted Hydrogen Evolution Reaction.

An efficient and facile water dissociation process plays a crucial role in enhancing the activity of alkaline hydrogen evolution reaction (HER). Considering the intricate influence between interfacial water and intermediates in typical catalytic systems, meticulously engineered catalysts should be developed by modulating electron configurations and optimizing surface chemical bonds. Here, a high-entropy double perovskite (HEDP) electrocatalyst La2(Co1/6Ni1/6Mg1/6Zn1/6Na1/6Li1/6)RuO6, achieving a reduced overpotential of 40.7mV at 10mA cm-2 and maintaining exemplary stability over 82 h in a 1m KOH electrolyte is reported. Advanced spectral characterization and first-principles calculations elucidate the electron transfer from Ru to Co and Ni positions, facilitated by alkali metal-induced super-exchange interaction in high-entropy crystals. This significantly optimizes hydrogen adsorption energy and lowers the water decomposition barrier. Concurrently, the super-exchange interaction enhances orbital hybridization and narrows the bandgap, thus improving catalytic efficiency and adsorption capacity while mitigating hysteresis-driven proton transfer. The high-entropy framework also ensures structural stability and longevity in alkaline environments. The work provides further insights into the formation mechanisms of HEDP and offers guidelines for discovering advanced, efficient hydrogen evolution catalysts through super-exchange interaction.

Super-exchange interaction enables Fe2−xMnxO3 perovskite with excellent catalytic oxidation activity toward hexabromocyclododecane under humidity

Although enhancing the catalytic oxidation activity is a hotspot in thermal-driven catalytic disposal of persistent organic pollutants, few studies have managed to improve catalysts' water-resistance properties. Herein, we developed Fe2−xMnxO3 perovskite to boost the catalytic oxidation of hexabromocyclododecane under humidity by modulating its super-exchange interaction (SEI, Fe3+ + Mn3+ → Fe2+ + Mn4+). Fe0.4Mn1.6O3, with the strongest SEI, exhibits the biggest oxidation rate-constant, which is 3 times higher than that of commonly used Fe2O3 without SEI. Notably, unlike Fe2O3 which deactivates at a relative humidity of 5 %. Fe0.4Mn1.6O3 maintains its activity and is even boosted by 22 % compared to dry conditions. Mechanistic insights reveal that SEI between Fe and Mn enhances the reactivity of Mn4+- linked Olatt by lowering the reductive temperature from Mn4+ to Mn3+. Meanwhile, SEI promotes the adsorption of the associatively adsorbed H2O (HOH-type water) by reducing adsorption energy, thereby facilitating the formation of hydroxyl species, which are crucial for the oxidation process under humidity.

Enhanced peroxymonosulfate activation for emerging contaminant degradation via defect-engineered interfacial electric field in FeNC

Peroxymonosulfate (PMS) activation technology has important application value in treating emerging contaminant (ECs), but it still faces challenges in achieving efficient electron transfer and metal valence cycling. In this study, the interfacial electric field characteristics of FeNC catalysts were adjusted by introducing NC defects to affect the electron transfer process, thereby enhancing the catalytic performance of PMS. It is found that in the FeNC structure, the shift of the charge generates an interfacial electric field, which can promote the directional transfer of electrons. Through quantitative structure–activity relationship (QSAR) analysis, it was confirmed that the defect played a decisive role in regulating the interfacial electric field and improving the catalytic reaction efficiency. The interfacial electric field-mediated superexchange interaction realizes the electron donor effect of organic pollutants and the effective electron transfer between the Fe site, accelerates the electron cycling of the Fe site, and realizes the rapid and stable catalysis of PMS. The increase of the occupancy state distribution of d orbitals near the Fermi level provides favorable conditions for electron transitions and catalytic activation of PMS. ECs can be converted into environmentally friendly, non-toxic and harmless substances through. This defect-controlled interface electric field strategy realizes rapid electron directional transfer, which provides a new solution for improving the catalytic efficiency of PMS and the safe treatment of ECs in water.

Prediction of Two-Dimensional Janus Transition-Metal Chalcogenides: Robust Ferromagnetic Semiconductor with High Curie Temperature.

Two-dimensional (2D) ferromagnetic semiconductors (FM SCs) provide an ideal platform for the development of quantum information technology in nanoscale devices. However, many developed 2D FM materials present a very low Curie temperature (TC), greatly limiting their application in spintronic devices. In this work, we predict two stable 2D transition metal chalcogenides, V3Se3X2 (X = S, Te) monolayers, by using first-principles calculations. Our results show that the V3Se3Te2 monolayer is a robust bipolar magnetic SC with a moderate bandgap of 0.53 eV, while V3Se3S2 is a direct band-gap FM SC with a bandgap of 0.59 eV. Interestingly, the ferromagnetisms of both monolayers are robust due to the V-S/Se/Te-V superexchange interaction, and TCs are about 406 K and 301 K, respectively. Applying biaxial strains, the FM SC to antiferromagnetic (AFM) SC transition is revealed at 5% and 3% of biaxial tensile strain. In addition, their high mechanical, dynamical, and thermal stabilities are further verified by phonon dispersion calculations and ab initio molecular dynamics (AIMD) calculations. Their outstanding attributes render the V3Se3Y2 (Y = S, Te) monolayers promising candidates as 2D FM SCs for a wide range of applications.

The Role of Rare-Earth Atoms in the Anisotropy and Antiferromagnetic Exchange Coupling at a Hybrid Metal-Organic Interface.

Magnetic anisotropy and magnetic exchange interactions are crucial parameters that characterize the hybrid metal-organic interface, a key component of an organic spintronic device. It is shown that the incorporation of 4f RE atoms to hybrid metal-organic interfaces of CuPc/REAu2 type (RE = Gd, Ho) constitutes a feasible approach toward on-demand magnetic properties and functionalities. The GdAu2 and HoAu2 substrates differ in their magnetic anisotropy behavior. Remarkably, the HoAu2 surface promotes the inherent out-of-plane anisotropy of CuPc, owing to the match between the anisotropy axis of substrate and molecule. Furthermore, the presence of RE atoms leads to a spontaneous antiferromagnetic exchange coupling at the interface, induced by the 3d-4f superexchange interaction between the unpaired 3d electron of CuPc and the 4f electrons of the RE atoms. It is shown that 4f RE atoms with unquenched quantum orbital momentum ( ), as it is the case of Ho, induce an anisotropic interfacial exchangecoupling.

Microwave-induced dual-responsive spinel (CoxMn1-xFe2O4) target-triggered non-radical pathways of peroxymonosulfate: Superexchange interaction and synergistic mechanism

The efficient activation of peroxymonosulfate (PMS) and the directional selection of oxidation pathways are crucial for achieving efficient pollutant removal in advanced oxidation processes (AOPs). A composite activation method of a microwave-induced dual-responsive catalyst (Co0.4Mn0.6Fe2O4) with both dielectric and catalytic properties is proposed to successfully trigger the non-radical pathway of PMS for 100 % removal of pharmaceutical pollutant (diatrizoate, DTZ) in 6 min, which shows good resistance to environmental interference and cyclic stability, and lower electrical energy requirement. 1O2 and surface-bound reactive oxygen species (ROS) are the main ROSs responsible for non-radical oxidation, with a total contribution of 98 %. The superexchange effect of Co-Mn (Mn3++Co3+→Mn4++Co2+) induces the electron delocalization of Mn site, which promotes the adsorption of PMS, interfacial charge transfer, and surface-bound ROS generation. The "thermal and non-thermal" effects of microwaves accelerate electron transfer and 1O2 generation to further trigger non-radical pathways. This work provides new strategies for bifunctional catalyst design and directional triggering of non-radical pathways of PMS-AOPs.

Tailoring the structural, magnetic and dielectric properties in holmium doped Ca-Ba hexaferrite nanoparticles by regulating the Ca-Ba (1:1) concentration for magnetic and electric applications

This work reports the synthesis and characterizations of holmium (Ho) doped Ba-Ca hexaferrites (Ba0.5Ca0.5Fe12-xHoxO19). Structural analysis confirms the pure hexagonal phase throughout, and morphology shows the uniformly distributed hexagonal-shaped particles. The incorporation of Ho3+ ions significantly enhanced magnetic properties, as evidenced by vibrating sample magnetometry (VSM), attributed to the reconfiguration of Fe3+ ions and the reinforcement of superexchange interactions. Across all samples, magnetic hysteresis (M−H) loops exhibited a consistent hard ferrimagnetic behavior, with saturation magnetization (Ms) values varying within the range of 28.64 to 36.33 emu/g, remanent magnetization (Mr) from 16.24 to 20.68 emu/g, and coercivity (Hc) from 1.771 to 2.059 kOe, respectively. The composition with x = 0.09 demonstrated the highest Ms, Mr, and Hc values. The dielectric properties underscore the potential applications of fabricated M−type hexaferrites in microwave technology due to their low dissipation factor and ε“, pivotal for minimizing signal attenuation in crucial components such as filters and resonators. Moreover, Ho doped Ba-Ca hexaferrites present promising alternatives to magnets in electric vehicle applications, suggesting avenues for further research and optimization in this domain.

Manipulating Superexchange Interaction of Ru–O–Fe Sites for Enhanced Electrocatalytic Nitrate-to-Ammonia Selectivity

Manipulating Superexchange Interaction of Ru–O–Fe Sites for Enhanced Electrocatalytic Nitrate-to-Ammonia Selectivity

Vanadium embedded in monolayer silicene: Energetics and proximity-induced magnetism

Using the density-functional theory approach, including Hubbard U correction, we investigate the defect structures consisting of vanadium (V) atoms embedded in a monolayer silicene. Specifically, we consider V–V atom pairs in antiferromagnetic (AFM), ferromagnetic (FM), and non-magnetic states, which are embedded in substitutional and interstitial sites. We determine the ground-state structures, formation and binding energies, electronic structures, induced magnetization, as well as the spin-exchange coupling between the V–V pair. For the substitutional vanadium atom pair, the stability of the AFM and FM spin configurations depends on the sublattice sites in which the V atoms are sited. When the V pair is located on a similar sublattice site type, the AFM spin alignment is more energetically favored, whereas when the pair is located in a different sublattice site, the FM interactions are more stable. However, the relative stability of the AFM or FM configurations changes rapidly as the separation between the V pair increases. Regarding the interstitial-hole V–V pair configurations, the most stable structure is when the pair is at the nearest-neighbor hole sites and is in an FM alignment. Also, at larger separations, the AFM or FM hole configurations are approximately degenerate in energy. Furthermore, we elucidate on the Ruderman–Kittel–Kasuya–Yosida, direct-exchange, and the superexchange interaction mechanisms in the vanadium-embedded silicene. In addition, we estimate a Curie temperature (Tc) of up to ∼500 K for a silicene structure containing a V pair in the FM spin alignment. Such a high Tc, in addition to the stability of the material, suggests that vanadium-embedded silicene is a potential candidate material for spintronic device applications.

Exploring the structural, magnetic, and dielectric properties of Fe and Y substituted NiCr2O4

This paper presents the successful single phase synthesis of NiCr2O4 and NiFe0.50Cr1.50-xYxO4 (x = 0 – 0.08) compounds followed by an investigation into their structural, magnetic and dielectric properties. The structural analysis confirms tetragonal structure for NiCr2O4 while a partially inverse cubic spinel structure for Fe and Y substituted samples (x = 0 – 0.08). Fe substitution (x = 0) induces a shift in room temperature hysteresis loop behaviour from paramagnetic to ferrimagnetic, suggesting enhanced superexchange interactions and a significant rise in magnetic transition temperature beyond room temperature. However, it is found that further inclusion of Y (x = 0.04 – 0.08) leads to a slight weakening of superexchange interactions. The saturation magnetization increases with Y substitution, while coercivity and magnetocrystalline anisotropy follows a decreasing trend. The complex impedance studies unveil a relaxation phenomenon and the dielectric constant is found to increase with the substitution of Fe and Y. Analysis of temperature dependent ac conductivity data and the frequency exponent profile suggests small polaron hopping as the predominant transport mechanism up to 380 K in NiCr2O4 and x = 0 samples, shifting to large polaron hopping beyond this temperature. In samples with x =0.04 and 0.06 the transport mechanism is found to follow the small polaron tunneling model. However, in the x = 0.08 sample, large polaron tunneling becomes predominant beyond 365 K.

The Role of Interfacial Interactions and Oxygen Vacancies in Tuning Magnetic Anisotropy in LaCrO3/LaMnO3 Heterostructures

AbstractThe interplay of lattice, electronic, and spin degrees of freedom at epitaxial complex oxide interfaces provides a route to tune their magnetic ground states. Unraveling the competing contributions is critical for tuning their functional properties. The relationship between magnetic ordering and magnetic anisotropy and the lattice symmetry, oxygen content, and film thickness in compressively strained LaMnO3 (LMO)/LaCrO3 (LCO) superlattices is investigated. Mn–O–Cr antiferromagnetic superexchange interactions across the heterointerface result in a net ferrimagnetic magnetic structure. Bulk magnetometry measurements reveal isotropic in‐plane magnetism for as‐grown oxygen‐deficient thin samples due to equal fractions of orthorhombic a+a‐c‐, and a‐a+c‐ twin domains. As the superlattice thickness is increased, in‐plane magnetic anisotropy emerges as the fraction of the a+a‐c‐ domain increases. On annealing in oxygen, the suppression of oxygen vacancies results in a contraction of the lattice volume, and an orthorhombic to rhombohedral transition leads to isotropic magnetism independent of the film thickness. The complex interactions are investigated using high‐resolution synchrotron diffraction and X‐ray absorption spectroscopy. These results highlight the role of the evolution of structural domains with film thickness, interfacial spin interactions, and oxygen‐vacancy‐induced structural phase transitions in tuning the magnetic properties of complex oxide heterostructures.